Novel metallized heterocyclic derivatives

ABSTRACT

The invention provides novel metal containing heterocyclic compounds useful as pigments.

United States Patent Lal Kaul July 22, 1975 [54] NOVEL METALLIZED HETEROCYCLIC [56] References Cited DERIVATIVES UNITED STATES PATENTS [75] Inventor: Bansi Lal Kaul, Basel. Switzerland 2,993,065 7/1961 Kumins et al 260/439 1731 Assignee= Sandoz Baseh Switzerland 333333;? 1211323 122282 ii 2 31:3.......::::3:.???/i%3 [221 Filed: FOREIGN PATENTS OR APPLICATIONS [21] Appl. No.: 317,518 1,416,293 9/1965 France 260/439 2,078,761 ll/l97l France 260/439 [30] Foreign Application Priority Data Pnmary Exammer.l0hn D. Randolph Dec. 31, 1971 Sw1tzerland 19258/71 J 28 1972 S l d 1317/72 Attorney, Agent, or Firm-Gerald D. Sharkm, R1chard an. wltzer an E. Vila; Joseph J. Bomvian [52] US. Cl. 260/240 G; 8/7; 8/62;

106/23; 106/288 Q; 117/38; 162/162; 260/39 1 ABSTRACT M The invention provides novel metal containing hetero- [51] Int. Cl C07d 51/02 cyclic compounds useful as pigments, [58] Field of Search 260/250 Q, 240 G, 242

18 Claims, No Drawings NOVEL METALLIZED HETEROCYCLIC DERIVATIVES This invention relates to metal containing heterocyclic compounds which are free from water-solubilising groups.

More particularly, this invention provides compounds of formula I,

in which the radicals R which may be the same or different, together with the carbon atoms to which they are attached, signify a carbocyclic or heterocyclic ring of aromatic character, the radicals R which may be the same or different, each signify a hydrogen atom or a substituent, R signifies a hydrogen atom or an alkyl or phenyl radical which may be substituted, Me signifies a divalent'metal atom, m signifies l or 2,

and n signifies l or 2 provided that the sum of n and m is at least 3 and that the compounds contain no carboxylic or sulphonic acid groups.

When R together with the carbon atoms to which it is attached, signifies an aromatic carbocyclic ring, it preferably signifies 1,2-phenylene, or 1,2 or 2,3- naphthalene. When R, together with the carbon atoms to which it is attached signifies a heterocyclic ring of aromatic character, such, for example, contains one or two oxygen, nitrogen or sulphur atoms. These aromatic rings may for example bear 1, 2, 3 or 4 substituents. Suitable substituents include halogen, in particular chlorine or bromine, alkyl of l to 8, preferablyl to 4 carbon atoms, trifluoromethyl, alkoxy of l to 8, preferably l to 4 carbon atoms, cyano, nitro, hydroxylamino, alkylamino or dialkylamino in which the alkyl group (s) contain 1 to 8, preferably 1 to 4 carbon atoms, or acyl. Preferred acyl groups are of formula R-Y or R--Z, in which R signifies a hydrocarbon radical which may be substituted, for example by any of the above men tioned substituents and may contain hetero atoms, e.g. oxygen, nitrogen or sulphur atoms, but is' preferably an alkyl radical of l to 8, preferably 1 to 4 carbon atoms,

in which R., signifies hydrogen or an alkyl radical of l to 8 carbon atoms or a phenyl radical which may be substituted, and R signifies an alkyl radical of l to 8 carbon atoms. R together with the carbon atoms to which it is attached, more preferably signifies a radical of formula II, III or lVa,

in which R, and R which may be the same or different, each signifies a hydrogen or halogen atom, or an alkyl or alkoxy radical of l to 4 carbon atoms, R, signifies a hydrogen atom, an alkyl radical of 1 to 4 carbon atoms, or the phenyl radical,

and R signifies an alkyl radical of l to 4 carbon atoms.

Suitable significances for R include hydrogen and those substituents mentioned above for the ring formed by R Suitably, each R signifies hydrogen or halogen, particularly chlorine or bromine or an alkyl or alkoxy radical of l to 4:-.carbon atoms. More preferably ,each R signifies a hydrogen atom.

Me suitably signifies a divalent metal atom such as chromium, manganese, iron, copper, zinc, nickel or cobalt, preferably copper, zinc, nickel or cobalt.

The formula [(NR ),,(CO),,,] suitably signifies the following radicals 4 When R signifies an alkyl radical, it preferably contains l to 8, more preferably 1 to 4 carbon atoms. Suitable substituents on such alkyl radicals, andon any other alkyl radicals present in the molecule include halogen, in particular chorine or bromine, cyano, alkoxy of l to 8, preferably l to 4 carbon atoms, phenyl, phenoxy, acyl, acyloxy and acylamino. Suitable such acyl radicals are those mentioned above. When R signifies phenyl it may suitably bear as substituents any of those mentioned above in connection with R Preferably, however, R signifies hydrogen, unsubstituted alkyl of l to 4 carbon atoms or phenyl, more preferably hydrogen.

The preferred compounds of formula I are those of formula la,

H II N N 2 1 CO 0 x 1," 1:1 p l I H on in which R, signifies a radical of formula V,

/H R8 HC XH V "-"rm in which R, and R,,, which may be the same or different, each signifies hydrogen, chlorine or methoxy, of formula VI,

CH CH HC C CH I II I v l-IC C or of formula VII,

H N R14 VI I in which R, is as defined above, Me signifies nickel,

cobalt, copper or zinc, and p signifies l or 2.

The invention also provides a process for the production of compounds of formula 1, characterised by metallising a compound of formula X,

4 U UH 5 N T2 OH [(NR (CO) in which R, R R n and m are as defined above, with a salt of the divalent metal Me.

The compounds of formula X are novel and may be produced by reacting a compound or compounds of formula VIII,

VIII

CI-IO in which R, is as defined above, with a compound of formula IX,

in which R R n and m are as defined above, or an acid addition salt thereof.

As will be appreciated, where the radicals R in the desired final product or compound X differ, then a mixture of compounds of formula VIII is employed.

As will also be appreciated, the metallisation of the compounds of formula X may be effected simultaneously with or subsequent to the reaction of the compound(s) VIII and the compound IX.

The condensation of the compound(s) VIII and compound IX is suitably effected in an aqueous medium or in an organic solvent which is miscible with water, e.g. an alkanol of l to 4 carbon atoms, dimethyl formamide, dimethyl acetamide, a glycol or glycol ether, dioxane or N-methylpyrrolidone. Suitably, the condensation is effected at a temperature of from room temperature to about 250C, preferably 30 to C. Suitable salts of the compound of formula lX include the hydrochloride or sulphate. As indicated, the reaction with the divalent metal salt may be effected simultaneously with the condensation. Alternatively, it may be effected subsequently in conventional manner. Suitable salts of the divalent metal include the chloride, formate and acetate.

The resulting compounds of formula I may be isolated and purified using conventional techniques.

The compounds of the invention are useful as pigments, particularly after conditioning by the normal methods for pigments. They are thus suitable for the pigmentation of synthetic polymeric materials in the mass. By this is understood, synthetic polymers and resins containing or free from solvents, including surface coatings on an oil or water basis, lacquers and enamels of various compositions and spinning solutions. The pigments are particularly applicable to viscose rayon, and cellulose acetate, polyethylene, polystyrene, polyvinyl chloride, rubber and poromerics (synthetic leather). The pigments are also suitable for use in printing inks, for dyeing paper in the stock, and for pigment EXAMPLE 1 A solution of 34.4 parts of 2-hydroxy-lnaphthaldehyde and 30 parts of 6,7-diamino-2,3- dihydroxyquinoxaline-dihydrochloride dihyd r ate in 3000 parts of dimethyl formamide is reacted for 2 hours at 140C with stirring. A solution of 12 parts of nickel chloride in 1000 parts of dimethyl formamide are added, after which the temperature is maintained at 140C for a further 2 hours with stirring. On cooling, yellowish red crystals settle out. The crystals are isolated by filtration, washed with dimethyl formamide and then with water, and dried, which frees the product from impurities and solvent. The pigment of formula H o N 7 I c o /N\;.4 N/CO W H I on EXAMPLE 2 A solution of 47.4 parts of 5,6-diamino-2-(3H)- benzimidazolone dihydrochloride in 400 parts of water is gradually combined over 30 minutes with a solution of 68.8 parts of 2-hydroxyl-l-naphthaldehyde in 1000 parts of 2-methoxyethanol, at room temperature, with stirring. Stirring is continued for 1 hour at room temperature, and the solution is reacted further for 1 hour at.'6 0 to with continued stirring. The crystalline orangev product of formula is filtered at room temperature, washed with methanol and dried.

47.2 parts of this compound are suspended in 1500 parts of dimethyl formamide. A solution of 12 parts of nickel chloride in I500 parts of dimethyl formamide is stirred into the suspension and the metallising reaction carried out for 2 hours at with stirring. On cooling to room temperature, the orange-red crystalline precipitate is filtered, washed with dimethyl formamide and then with water, and dried. The pigment thus formed which is the nickel derivative of the above compound pigments polyvinyl chloride in intense orange shades which show satisfactory fastness properties.

The same pigment can be produced as follows. A mixture of 24.6 parts of 5,6 diamino-2-( 3H)- benzimidazolone and 51.6 parts of 2-hydroxy-lnaphthaldehyde in 750 parts of dimethyl formamide is reacted for 1 hour at 23 and then for 1 hour at 60 with constant stirring. A clear solution of orange colour is formed which is cooled to 25 and set with 35.5 parts of nickel chloride hexahydrate, added with continued stirring. The reaction mixture is raised to 125 and held at this temperature for 2 hours with stirring. The orange-red pigment is filtered from the hot medium, washed with dimethyl formamide, then with water and finally with ethanol, and dried.

The pigments specified in the table below may be produced in analogy with the procedures of Example 1 or 2 and are identified in the table by the significance of the symbols in formula I and by their shades in polyvinyl chloride.

TABLE Exa- Shade in p R [(NR ),,(CO),,,] Me Polyvinyl Nr. chloride I NH 3 H Ni yellowf0 orange CO NH 4 do. H do. Co brown 5 C1 H do. Ni brown 6 do. H do. Cu yellow 7 H do. Cu orange 8 do. H NH Zn yellow- CO orange NH 9 do. H do. Cu brownorange lO H do. Cu browngelb ll do. H do. Co yelloworange 12 p H NH Zn yellow NH 13 p H do. Cu yellow 14 Haco 1% H do. Ni orange 15 do. H do. Zn yellow 16 C1 H do. Cu yelloworange 1* Cl l7 do. H do. Ni orange 18 do. H do. Zn yellow 19 O H do. Zn do.

I H3C 20 N c o H do. Ni redorange N-CH l 3 H C 21 0 H do. Zn do.

N-C H 22 0 H do. Cu brownorange to rotate at 20 and 25 r.p.m. respectively to exert frictional force for improved pigment distribution. The

mixture is extruded as film of 0.3 mm thickness, which is pigmented in a yellowish red shade showing satisfactory light and migration fastness and heat stability.

Similar results may be obtained with the pigments of any of the other foregoing Examples.

What is claimed is:

1. A compound of formula in which the radicals R which may be the same or different, together with the carbon atoms to which they are attached, each signifies an unsubstituted or mono-, di-, trior tetra-substituted carbocyclic radical selected from the group consisting of 1,2- phenylene, 1,2-naphthalene and 2,3-napthalene, or a heterocyclic radical of the formula in which R, signifies hydrogen or an alkyl radical of 1 to 8 carbon atoms or a phenyl radical and R signifies an alkyl radical of l to 8 carbon atoms,

each R is hydrogen, halogen or alkyl or alkoxy of l to 4 carbon atoms,

[(NR ),,(CO),,,] signifies a radical selected from R signifies hydrogen, an alkyl radical of l to 8 carbon atoms, which is unsubstituted or substituted by halogen, cyano, alkoxy of 1 to 8 carbon atoms, phenyl, phenoxy, acyl, acylamino or acyloxy, or a phenyl radical which is unsubstituted or mono-, dior tri-substituted,

Me signifies chromium, manganese, iron, copper,

zinc, nickel or cobalt,

m signifies l or 2,

and n signifies l or 2,

provided that the sum of n and m is at least 3 and that the compounds contain no carboxylic or sulphonic acid groups,

and further provided that any substituent on a carbocyclic significance of R or on the phenyl significance of R is selected from the group consisting of halogen, alkyl or alkoxy of l to 8 carbon atoms, trifluoromethyl, cyano, nitro, hydroxylamine, alkylamino or dialkylamino in which the alkyl radical(s) contain 1 to 8 carbon atoms, and acyl, and further provided that any acyl radical is selected from the group consisting of alkoxycarbonyl and alkanoyl in which the alkyl radical contains l to 4 carbon atoms, alkylsulphonyl or alkoxysulphonyl of 1 to 4 carbon atoms, phenylsulphonyl, benzoyl, phenoxycarbonyl, phenoxysulphonyl and alkylaminocarbonyl and dialkylaminocarbonyl in which the alkyl radical(s) contain 1 to 4 carbon atoms.

2. A compound of claim 1, in which the radicals R are the same.

3. A compound of claim 1, in which the substituents are selected from chlorine, bromine, alkyl or alkoxy of l to 4 carbon atoms, trifluoromethyl, cyano, nitro, hydroxylamino, alkyl or dialkylamino, in which the alkyl radical(s) contain 1 to 4 carbon atoms, oxo, alkoxycarbonyl and alkanoyl in which the alkyl radical contains 1 to 4 carbon atoms, alkylsulphonyl or alkoxysulphonyl of l to 4 carbon atoms, phenylsulphonyl, benzoyl, phenoxycarbonyl, phenoxysulphonyl and alkylaminocarbonyl and dialkylaminocarbonyl in which the alkyl radical(s) contain 1 to 4 carbon atoms.

4. A compound of claim 1, in which the radicals R together with the carbon atoms to which they are attached, each signify a radical of formula II, III or lVa,

IVa

in which R and R which may be the same or different, each signifies a hydrogen or halogen atom, or an alkyl or alkoxy radical of l to 4 carbon atoms, R, signifies a hydrogen atom, or an alkyl radical of 1 to 4 carbon atoms, or the phenyl radical,

and R signifies an alkyl radical of l to 4 carbon atoms. 5. A compound of claim 1, in which each R is hydrogen.

6. A compound of claim 1, in which Me signifies copper, zinc, nickel or cobalt.

7. A compound of claim 1, in which R signifies hydrogen, unsubstituted alkyl of l to 4 carbon atoms, or unsubstituted phenyl.

8. A compound of claim 1, in which R signifies hydrogcn.

9. A compound of claim 1 of formula I I H I O N \M Ia e I l O J 1;; p

H H CH in which R signifies a radical of formula V,

CHXRB' HC (IIH V R in which R-,' and R which may be the same or different, each signifies hydrogen, chlorine or methoxy, of formula VI,

CH H l HC C CH I II I w HC C or of formula VII,

in which R is hydrogen, alkyl of l to 4 carbons or phenyl Me signifies nickel, cobalt, copper or zinc,

and p signifies I or 2.

10. A compound of claim 9 of formula 11. A compound of claim 9 of formula 12. A compound of claim 9 of formula 13. A compound of claim 9 of formula 14. A compound of formula in which the radicals R which may be the same or different, together with the carbon atoms to which they are attached, each signifies an unsubstituted or mono-, di-, trior tetra-substituted carbocyclic radical selected from the group consisting of 1,2- phenylene, 1,2-naphthalene and 2,3-naphthalene, or a heterocyclic radical of the formula in which R, signifies hydrogen or an alkyl radical of l to 8 carbon atoms or a phenyl radical and R signifies an alkyl radical of l to 8 carbon atoms,

each R is hydrogen, halogen or alkyl or alkoxy of l to 4 carbon atoms,

[(NR ),,(CO),,,]signifies a radical selected from R signifies hydrogen, an alkyl radical of 1 to 8 carbon atoms, which is unsubstituted or substituted by halogen, cyano, alkoxy of 1 to 8 carbon atoms, phenyl, phenoxy, acyl, acylamino or acyloxy, or a phenyl radical which is unsubstituted or mono-, dior tri-substituted,

m signifies l or 2,

and n signifies l or 2,

provided that the sum of n and m is at least 3 and that the compounds contain no carboxylic or sulphonic acid groups,

and further provided that any substituent on a carbocyclic significance of R or on the phenyl significance of R is selected from the group consisting of halogen, alkyl or alkoxy of l to 8 carbon atoms, trifluoromethyl, cyano, nitro, hydroxylamine, alkylamino or dialkylamino in which the alkyl radical(s) contain 1 to 8 carbon atoms, and acyl,

and further provided that any acyl radical is selected from the group consisting of alkoxycarbonyl and alkanoyl in which the alkyl radical contains 1 to 4 carbon atoms, alkylsulphonyl or alkoxysulphonyl of 1 to 4 carbon atoms, phenylsulphonyl, benzoyl, phenoxycarbonyl, phenoxysulphonyl and alkylaminocarbonyl and dialkylaminocarbonyl in which the alkyl radical(s) contain l to 4 carbon atoms.

15. A compound of claim 14 of formula 16. A compound of claim 14 of formula 17. A compound according to claim 4 wherein the radicals R are the same, R is hydrogen, R is hydrogen, alkyl of l to 4 carbons or phenyl, and the radical 3)n( )m] NR N l 3 3\ O or C O o Nk NR 18. A compound according to claim 9 wherein R is a radical of formula VI. 

1. A COMPOUND OF FORMULA
 2. A compound of claim 1, in which the radicals R1 are the same.
 3. A compound of claim 1, in which the substituents are selected from chlorine, bromine, alkyl or alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano, nitro, hydroxylamino, alkyl or dialkylamino, in which the alkyl radical(s) contain 1 to 4 carbon atoms, oxo, alkoxycarbonyl and alkanoyl in which the alkyl radical contains 1 to 4 carbon atoms, alkylsulphonyl or alkoxysulphonyl of 1 to 4 carbon atoms, phenylsulphonyl, benzoyl, phenoxycarbonyl, phenoxysulphonyl and alkylaminocarbonyl and dialkylaminocarbonyl in which the alkyl radical(s) contain 1 to 4 carbon atoms.
 4. A compound of claim 1, in which the radicals R1, together with the carbon atoms to which they are attached, each signify a radical of formula II, III or IVa,
 5. A compound of claim 1, in which each R2 is hydrogen.
 6. A compound of claim 1, in which Me signifies copper, zinc, nickel or cobalt.
 7. A compound of claim 1, in which R3 signifies hydrogen, unsubstituted alkyl of 1 to 4 carbon atoms, or unsubstituted phenyl.
 8. A compound of claim 1, in which R3 signifies hydrogen.
 9. A compound of claim 1 of formula
 10. A compound of claim 9 of formula
 11. A compound of claim 9 of formula
 12. A compound of claim 9 of formula
 13. A compound of claim 9 of formula
 14. A compound of formula
 15. A compound of claim 14 of formula
 16. A compound of claim 14 of formula
 17. A compound according to claim 4 wherein the radicals R1 are the same, R2 is hydrogen, R3 is hydrogen, alkyl of 1 to 4 carbons or phenyl, and the radical >((NR3)n(CO)m)is
 18. A compound according to claim 9 wherein R5 is a radical of formula VI. 